Partitioning of rare earth and high field strength elements between titanite and phonolitic liquid

We present the results of a LA–ICPMS study of titanites and associated glasses from the mixed-magma phonolitic Fasnia Member of the Diego Hernández Formation, Tenerife, Canary Islands. We employ a method of identifying equilibrium mineral–melt pairs from natural samples using REE contents and a linear form of the lattice strain model equation (Blundy and Wood, 1994), where the Young's modulus (E_M) for the 7-fold coordinated site is an output variable. For felsic magmas that contain crystals potentially derived from a variety of environments within the system, this approach is more rigorous than the use of solely textural criteria such as mineral–glass proximity. We then estimate titanite/melt partition coefficients for Y, Zr, Nb, REE, Hf, Ta, U and Th. In common with prior studies, we find that middle REE partition more strongly into titanite than either light or heavy REE, and that REE partitioning behavior in titanite is reasonably predicted by the lattice strain model. Titanite also fractionates Y from Ho, Zr from Hf, and Nb from Ta. Comparison with experimental data indicates that melt structure effects on partitioning are significant, most particularly in very highly polymerized melts. We use the data to estimate 7-fold coordination radii for trivalent Pr, Nd, Ho, Tm and Lu, and to make approximate predictions of titanite/melt partitioning of Ra, Ac and Pa. Interpolation of data for heavy REE does not predict the behavior of Y, indicating that factors other than charge and radius are involved in partitioning. Variations in Y/Ho induced by magmatic processes appear to be negatively correlated with temperature, and are expected to be greatest in near-minimum melts.     

Equilibrium vs. disequilibrium melting relations in theHigher Himalayan Crystalline (HHC) pelitic migmatites,Sikkim Himalaya

Higher Himalayan Crystalline (HHC) complex of the Sikkim Himalaya predominantly consists of high-grade pelitic migmatites. In this study, reaction textures, mineral/bulk rare earth elements (REE), trace element partition coefficients and trace element zoning profiles in garnet are used to demonstrate a complex petrogenetic process during crustal anatexis. With the help of equilibrium REE and trace element partitioning model, it is shown that strong enrichment of Effective Bulk Composition (EBC) is responsible for the zoning in garnet in these rocks. The data strongly support disequilibrium element partitioning and suggest that the anatectic melts associated with mafic selvedges are likely produced by disequilibrium melting because of fast melt segregation process.     

Experimental comparison of trace element partitioning between clinopyroxene and melt in carbonate and silicate systems, and implications for mantle metasomatism

Experiments in the systems diopside-albite (Di-Ab) and diopside-albite-dolomite (Di-Ab-Dmt), doped with a wide range of trace elements, have been used to characterise the difference between clinopyroxene-silicate melt and clinopyroxene-carbonate melt partitioning. Experiments in Di-Ab-Dmt yielded clinopyroxene and olivine in equilibrium with CO₂-saturated dolomitic carbonate melt at 3 GPa, 1375 °C. The experiments in Di-Ab were designed to bracket those conditions (3 GPa, 1640 °C and 0.8 GPa, 1375 °C), and so minimise the contribution of differential temperature and pressure to partitioning. Partition coefficients, determined by SIMS analysis of run products, differ markedly for some elements between Di-Ab and Di-Ab-Dmt systems. Notably, in the carbonate system clinopyroxene-melt partition coefficients for Si, Al, Ga, heavy REE, Ti and Zr are higher by factors of 5 to 200 than in the silicate system. Conversely, partition coefficients for Nb, light REE, alkali metals and alkaline earths show much less fractionation (<3). The observed differences compare quantitatively with experimental data on partitioning between immiscible carbonate and silicate melts, indicating that changes in melt chemistry provide the dominant control on variation in partition coefficients in this case. The importance of melt chemistry in controlling several aspects of element partitioning is discussed in light of the energetics of the partitioning process. The compositions of clinopyroxene and carbonate melt in our experiments closely match those of near-solidus melts and crystals in CMAS-CO₂ at 3 GPa, suggesting that our partition coefficients have direct relevance to melting of carbonated mantle lherzolite. Melts so produced will be characterised by elevated incompatible trace element concentrations, due to the low degrees of melting involved, but marked depletions of Ti and Zr, and fractionated REE patterns. These are common features of natural carbonatites. The different behaviour of trace elements in carbonate and silicate systems will lead to contrasted styles of trace element metasomatism in the mantle. Received: 15 July 1999 / Accepted: 18 February 2000     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

Surface-structure-controlled sectoral zoning of the rare earth elements in fluorite from Long Lake, New York, and Bingham, New Mexico, USA

The concentration and distribution of rare earth elements (REE) in sectorally zoned fluorite crystals from Long Lake, New York, and the Hansonburg Mining District, Bingham, New Mexico, have been studied using cathodoluminescence and synchrotron X-ray fluorescence microanalysis (SXRFMA). In cubo-octahedral samples from Long Lake, New York, Ce, Nd, Gd, Dy, Ho, Er, and Tm are preferentially partitioned into the |111| sector relative to the |100| sector. Partition coefficients (K_d = concentration in |111| sector/concentration in |100| sector) range between 3.5 for Ce, to 1.4 for Tm, with a general decrease in K_d as elements deviated from the ionic radius of Ca²⁺, for which REE substitute in fluorite. Diffusion of the REE has occurred, as evidenced by gradual changes in composition over distances of 0.2 to 0.3 mm at sector boundaries.In Bingham samples, three different partition coefficients were determined for Dy: K_d|100|/|111| = 2.83, K_{d |100|/|110|} = 1.77, and K_{d |110|/|111|} = 1.60. These are mean K_d values for a 95% confidence interval. In another sample from the same deposit, Dy, Er, and Gd were found to be preferentially incorporated into the |100| sector relative to the |210| sector with average K_{d |100|/|210|} of 3.1, 2.4, and 2.9, respectively. In a third sample, Nd was found to be preferentially incorporated into the |110| sector relative to the |321| sector with an average K_{d |110|/|321|} value of 2.3.Compositional heterogeneities in a given sector (concentric zoning) have been resolved using SXRFMA but are significantly less than the concentration difference across sector boundaries. Often fluorite exists in a wide variety of morphologies, as is the case in the Hansonburg Mining District of Bingham. We suggest caution when using the REE as petrogenetic indicators because fluorite trace element chemistry can vary greatly among crystals within a deposit depending on the internal morphology of a particular crystal.     

The importance of adsorption in igneous partitioning of trace elements

For accurate mathematical modeling of trace-element partitioning during igneous fractionation, adsorption should be considered. Because of adsorption, the partitioning of elements between liquid and a surface layer of a crystal is often not the same as the partitioning between liquid and the solid crystal at true equilibrium. In some minerals e.g. high-calcium pyroxene, the effect of adsorption during crystal growth may be very important; this is suggested by the frequent occurrence of sector zoning in augite, and the wide range in measured partition coefficients for such elements as rare earths. The ions which are enriched by adsorption are usually those which are favored substituents according to Goldschmidt's rules. In other minerals, uptake of trace elements may be closer to equilibrium partitioning, rather than being determined by kinetic factors. For example, the relative partitioning of REE, U, Th and Pb into feldspars is qualitatively predicted by Pauling's rules for complex ionic crystals, rather than by Goldschmidt's rules.     

Experimentally determined mineral-melt partition coefficients for Sc,Y and REE for olivine,orthopyroxene, pigeonite,magnetite and ilmenite

Our current lack of understanding of the partitioning behavior of Sc, Y and the REE (rare-earth elements) can be attributed directly to the lack of a sufficiently large or chemically diverse experimental data set. To address this problem, we conducted a series of experiments using several different natural composition lavas, doped with the elements of interest, as starting compositions. Microprobe analyses of orthopyroxene, pigeonite, olivine, magnetite, ilmenite and co-existing glasses in the experimental charges were used to calculate expressions that describe REE partitioning as a function of a variety of system parameters. Using expressions that represent mineral-melt reactions (versus element ratio distribution coefficients) it is possible to calculate terms that express low-Ca pyroxene-melt partitioning behavior and are independent of both pyroxene and melt composition. Compositional variations suggest that Sc substitution in olivine involves either a paired substitution with Al or, more commonly, with vacancies. The partitioning of Sc is dependent both on melt composition and temperature. Our experimentally determined olivine-melt REE Ds (partition coefficients) are similar to, but slightly higher than those reported by McKay (1986) and support their conclusions that olivines are strongly LREE depleted. Y and REE mineral/melt partition coefficients for magnetite range from 0.003 for La to 0.02 for Lu. Ilmenite partition coefficients range from 0.007 for La to 0.029 for Lu. These experimental values are two orders of magnitude lower than many of the published values determined by phenocryst/matrix separation techniques.     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

Rare earth and high field strength element partitioning between iron-rich clinopyroxenes and felsic liquids

Rare earth elements are commonly assumed to substitute only for Ca in clinopyroxene because of the similarity of ionic radii for REE³⁺ and Ca²⁺ in eightfold coordination. The assumption is valid for Mg-rich clinopyroxenes for which observed mineral/melt partition coefficients are readily predicted by the lattice strain model for substitution onto a single site (e.g., Wood and Blundy 1997). We show that natural Fe-rich pyroxenes in both silica-undersaturated and silica-oversaturated magmatic systems deviate from this behavior. Salites (Mg# 48–59) in phonolites from Tenerife, ferrohedenbergites (Mg# 14.2–16.2) from the rhyolitic Bandelier Tuff, and ferroaugites (Mg# 9.6–32) from the rhyolitic Rattlesnake Tuff have higher heavy REE contents than predicted by single-site substitution. The ionic radius of Fe²⁺ in sixfold coordination is substantially greater than that of Mg²⁺; hence, we propose that, in Fe-rich clinopyroxenes, heavy REE are significantly partitioned between eightfold Ca sites and sixfold Fe and Mg sites such that Yb and Lu exist dominantly in sixfold coordination. We also outline a REE-based method of identifying pyroxene/melt pairs in systems with multiple liquid and crystal populations, based upon the assumption that LREE and MREE reside exclusively in eightfold coordination in pyroxene. Contrary to expectations, interpolation of mineral/melt partition coefficient data for heavy REE does not predict the behavior of Y. We speculate that mass fractionation effects play a role in mineral/melt lithophile trace element partitioning that is detectable among pairs of isovalent elements with near-identical radii, such as Y and Ho, Zr and Hf, and Nb and Ta.     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D ₀, r ₀ and E) as functions of pressure, temperature, and compositions of cpx and melt. D ₀ is found to positively correlate with Al in tetrahedral site (Al ^T ) and Mg in the M2 site (Mg^M2) of cpx and negatively correlate with temperature and water content in the melt. r ₀ is negatively correlated with Al in M1 site (Al^M1) and Mg^M2 in cpx. And E is positively correlated with r ₀. During adiabatic melting of spinel lherzolite, temperature, Al ^T , and Mg^M2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.     

Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

Plagioclase zoning in the setogawa ash-flow sheet of the Nohi rhyolite complex,central Japan

Single whole crystals of calcic augite from M. Etna, Sicily, which display both sector and oscillatory zoning, have been serially sectioned and the form of the sectors mapped out. The principal intersectorial chemical variation is shown to be that of Ti and Al by as much as 39% (cation %) change in each, and the least variation, that of Ca (showing a 0.77 to 3.20% change). For each of three isochronous surfaces the ratio of Ti∶Al is shown to be individually constant no matter what the sector and this is thought to indicate near equilibrium conditions at the crystal/liquid interface. In addition to sector zoning these crystals display two types of concentric banding, having dimensions of about 0.25 mm, 20 μm. The 20 μm banding is shown to be both optically and chemically oscillated. Relative diffusion rates of cationic species in the melt, and growth rates of crystal faces are thought to play an important role in the formation of the oscillations, and the sector zoning.     

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.     

A parameterized model for REE distribution between low-Ca pyroxene and basaltic melts with applications to REE partitioning in low-Ca pyroxene along a mantle adiabat and during pyroxenite-derived melt and peridotite interaction

Low-Ca pyroxenes play an important role in mantle melting, melt-rock reaction, and magma differentiation processes. In order to better understand REE fractionation during adiabatic mantle melting and pyroxenite-derived melt and peridotite interaction, we developed a parameterized model for REE partitioning between low-Ca pyroxene and basaltic melts. Our parameterization is based on the lattice strain model and a compilation of published experimental data, supplemented by a new set of trace element partitioning experiments for low-Ca pyroxenes produced by pyroxenite-derived melt and peridotite interaction. To test the validity of the assumptions and simplifications used in the model development, we compared model-derived partition coefficients with measured partition coefficients for REE between orthopyroxene and clinopyroxene in well-equilibrated peridotite xenoliths. REE partition coefficients in low-Ca pyroxene correlate negatively with temperature and positively with both calcium content on the M2 site and aluminum content on the tetrahedral site of pyroxene. The strong competing effect between temperature and major element compositions of low-Ca pyroxene results in very small variations in REE partition coefficients in orthopyroxene during adiabatic mantle melting when diopside is in the residue. REE partition coefficients in orthopyroxene can be treated as constants at a given mantle potential temperature during decompression melting of lherzolite and diopside-bearing harzburgite. In the absence of diopside, partition coefficients of light REE in orthopyroxene vary significantly, and such variations should be taken into consideration in geochemical modeling of REE fractionation in clinopyroxene-free harzburgite. Application of the parameterized model to low-Ca pyroxenes produced by reaction between pyroxenite-derived melt and peridotite revealed large variations in the calculated REE partition coefficients in the low-Ca pyroxenes. Temperature and composition of starting pyroxenite must be considered when selecting REE partition coefficients for pyroxenite-derived melt and peridotite interaction.     

Chemical differentiation of the Cordillera Paine granite (southern Chile) by in situ fractional crystallization

Geochemical and field data for the Cordillera Paine (CP) pluton of southern Chile, indicate that differentiation took place by closed system in situ fractional crystallization. Minor, local and irregular separation of liquids from crystals led to the formation of evolved granites and aplites which are encountered mostly at the plutons roof and margins. Chemical trends show strong depletions of Sr, Ba, Mg less intense depletions of Ca, La, Ce, Nd, Fe, Ti, Al and enrichment of Nb, Y, Th, Rb and Si with differentiation. Pronounced crystal zoning of Ca, Sr and Ba in plagioclase, Ba in orthoclase and LREE, Y and Th in allanite closely correspond to the whole rock chemical variation. The crystal zoning data suggest that surface equilibrium only was maintained for the zoned elements during crystallization. Thus, continuous separation of liquids from crystals was not necessary to generate the kind highly evolved differentiates whose character reflects fractional crystallization. The schedule of liquid-crystal separation affects mainly the location, degree of dispersion and relative abundance of the differentiates. The homogeneity of the CP pluton and the intense crystal zoning suggest that crystal-liquid separation was inefficient, and that whole rock compositions approach liquid compositions. Assumption of a closed system during crystallization allows estimation of mineral/melt partition coefficients (K _d s) using crystal core and whole rock compositions. Crystal zoning and whole rock chemical trends are consistent with models constructed using the K _d s thus obtained along with modal abundances from petrographic estimates. Lamont-Doherty Geological Observatory Contribution Number 3701     

矿物—熔体间元素分配系数资料及主要变化规律

本文提供了不同成分的8大类主岩(偏铝质(超)基性岩、过碱性(超)基性岩、偏铝质中性岩、过碱性中性岩、偏铝质酸性岩、过碱性酸性岩、过铝质酸性岩、超酸性岩)中28个矿物(橄榄石、单斜辉石、斜方辉石、角闪石、黑云母、金云母、斜长石、钾长石、石英、磁铁矿、钛铁矿、石榴石、锆石、磷灰石、绿帘石、黄玉、榍石、堇青石、蓝方石、石榴石、霞石、白磷钙矿、镁铁钛矿、板钛矿、黄长石、钙钛矿、尖晶石、金红石)的69个化学元素(Li、Rb、Cs、K、Na、Ca、Sr、Ba、Mn、Fe、Mg、Cu、Pb、Zn、Co、Ni、Be、La、Ce、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y、Sc、Cr、In、Ga、Al、B、Cd、Sb、Bi、U、Th、Zr、Hf、Si、Ti、Ge、Sn、Mo、Nb、Ta、W、V、P、F、Cl、S、N、O、C、As、Pu、Re、Os、He、Ne、Ar、Xe、Kr)和1个化学一价原子团OH的分配系数。综合分析对比表明,矿物、熔体的成分和结构是分配系数的最重要的控制因素。对前人未讨论过的矿物结构和熔体铝过饱和度这两个因素应引起重视。最后,本文分析了矿物-熔体间元素分配系数的研究现状、存在问题,指出了这一领域今后的研究方向。     

Extension of lattice strain theory to mineral/mineral rare-earth element partitioning: An approach for assessing disequilibrium and developing internally consistent partition coefficients between olivine, orthopyroxene, clinopyroxene and basaltic melt

Olivine/melt and orthopyroxene/melt rare-earth element (REE) partition coefficients consistent with clinopyroxene/melt partition coefficients were determined indirectly from subsolidus partitioning between olivine, orthopyroxene, and clinopyroxene after suitable correction for temperature. Heavy- and middle-REE ratios for olivine/clinopyroxene and orthopyroxene/clinopyroxene pairs correlate negatively with effective cationic radius, whereas those for the light REEs correlate positively with cationic radius, generating a U-shaped pattern in apparent mineral/clinopyroxene partition coefficients versus cationic radius. Lattice strain models of partitioning modified for subsolidus conditions yield negative correlations of olivine/clinopyroxene and orthopyroxene/clinopyroxene with respect to cationic radii, predicting well the measured partitioning behaviors of the heavy and middle REEs but not that of the light REEs. The light-REE systematics cannot be explained with lattice strain theory and, instead, can be explained by disequilibrium enrichment of the light REEs in melt inclusions or on the rims of olivine and orthopyroxene. Realistic light-REE partition coefficients were thus extrapolated from the measured heavy- and middle-REE partition coefficients using the lattice strain model. Light REE olivine/melt and orthopyroxene/melt partition coefficients calculated in this manner are lower than most published values, but agree reasonably well with partitioning experiments using the most recent in situ analytical techniques (secondary-ionization mass spectrometry and laser ablation inductively coupled plasma mass spectrometry). These new olivine/melt and orthopyroxene/melt partition coefficients are useful for accurate modeling of the REE contents of clinopyroxene-poor to -free lithologies, such as harzburgitic residues of melting. Finally, the application of the lattice strain theory to subsolidus conditions represents a framework for assessing the degree of REE disequilibrium in a rock.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Experimental and computational study of trace element distribution between orthopyroxene and anhydrous silicate melt: substitution mechanisms and the effect of iron

Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 Although orthopyroxene (Opx) is present during a wide range of magmatic differentiation processes in the terrestrial and lunar mantle, its effect on melt trace element contents is not well quantified. We present results of a combined experimental and computational study of trace element partitioning between Opx and anhydrous silicate melts. Experiments were performed in air at atmospheric pressure and temperatures ranging from 1,326 to 1,420°C in the system CaO–MgO–Al₂O₃–SiO₂ and subsystem CaO–MgO–SiO₂. We provide experimental partition coefficients for a wide range of trace elements (large ion lithophile: Li, Be, B, K, Rb, Sr, Cs, Ba, Th, U; rare earth elements, REE: La, Ce, Nd, Sm, Y, Yb, Lu; high field strength: Zr, Nb, Hf, Ta, Ti; transition metals: Sc, V, Cr, Co) for use in petrogenetic modelling. REE partition coefficients increase from $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 $ D_{\text{La}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.0005 to $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 $ D_{\text{Lu}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.109 , D values for highly charged elements vary from $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 $ D_{\text{Th}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0026 through $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 $ D_{\text{Nb}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0033 and $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 $ D_{\text{U}}^{{{\text{Opx}} {\hbox{-}} {\text{melt}}}} \sim 0.0066 to $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 $ D_{\text{Ti}}^{{\text{Opx}} {\hbox{-}} {\text{melt}}} \sim 0.058 , and are all virtually independent of temperature. Cr and Co are the only compatible trace elements at the studied conditions. To elucidate charge-balancing mechanisms for incorporation of REE into Opx and to assess the possible influence of Fe on Opx-melt partitioning, we compare our experimental results with computer simulations. In these simulations, we examine major and minor trace element incorporation into the end-members enstatite (Mg₂Si₂O₆) and ferrosilite (Fe₂Si₂O₆). Calculated solution energies show that R²⁺ cations are more soluble in Opx than R³⁺ cations of similar size, consistent with experimental partitioning data. In addition, simulations show charge balancing of R³⁺ cations by coupled substitution with Li⁺ on the M1 site that is energetically favoured over coupled substitution involving Al–Si exchange on the tetrahedrally coordinated site. We derived best-fit values for ideal ionic radii r ₀, maximum partition coefficients D ₀, and apparent Young’s moduli E for substitutions onto the Opx M1 and M2 sites. Experimental r ₀ values for R³⁺ substitutions are 0.66–0.67 ? for M1 and 0.82–0.87 ? for M2. Simulations for enstatite result in r ₀ = 0.71–0.73 ? for M1 and ~0.79–0.87 ? for M2. Ferrosilite r ₀ values are systematically larger by ~0.05 ? for both M1 and M2. The latter is opposite to experimental literature data, which appear to show a slight decrease in $ r_{0}^{{{\text{M}}2}} $ r_{0}^{{{\text{M}}2}} in the presence of Fe. Additional systematic studies in Fe-bearing systems are required to resolve this inconsistency and to develop predictive Opx-melt partitioning models for use in terrestrial and lunar magmatic differentiation models.